Patent GB-848400-A (GB)
Title: Copolymers of unsaturated polyester resins and process for the production thereof
Inventor: WILLERSINN HERBERT
IPC: C09D4/00
Filed: 1959-06-01
Abstract: A hard glossy copolymer is obtained by copolymerising through unsaturated ethylenic linkages a homogenous mixture of (A) an unsaturated polyester resin of an alpha-betaunsaturated polycarboxylic acid and a saturated polyhydric alcohol and (B) a solvent-soluble condensation product of an ether from a beta gamma-ethylenically unsaturated alcohol and a methylol glyoxal diureine, with itself or with a compound containing at least, and preferably two reactive groups which are hydroxy and/or carboxy groups, the condensation product containing at least, and preferably two diureine units per molecule and having at least two beta gamma ethylenically unsaturated ether groups per diureine unit.  The preferred initial materials prior to their polycondensation with each other or with a minor proportion of saturated polyhydroxy or polycarboxy compounds have the formula :  <FORM:0848400/IV(a)/1> where R is hydrogen, lower alkyl, cycloalkyl or phenyl radical and R1 is the hydrocarbon residue of a beta gamma ethylenically unsaturated monohydric alcohol.  The nitrogen atom of the diureine is attached to the methylene group, this with the oxygen, and this in term with the radical of the beta gamma unsaturated alcohol remaining after etherification by splitting off water between the hydroxyl group of the beta-gamma unsaturated alcohol and the hydroxyl group of the methylol group.  Suitable radicals of the betagamma unsaturated alcohol are allyl, methallyl, crotyl, cyclohexenyl or cyclopentenyl radicals.  Condensation may be effected between 40 and 180 DEG  C using as catalyst, hydrochloric acid, nitric acid, phosphoric acid, sulphuric acid, sulphurous acid, para-toluene sulphonic acid, phthalic acid, formic acid, oxalic acid, acetic acid, chlorinated acetic acid, sodium hydrogen sulphate, primary sodium phosphate, ammonium nitrate or ammonium phosphate.  The polymerisable mixture of unsaturated polyester resin and condensation products from beta gamma unsaturated ethers of methylol duireines may be copolymerised with styrene, alkyl styrene, halogen styrenes, divinyl benzenes, vinyl naphthalene, vinyl pyridine, N-vinyl carbazole, vinyl methyl ketone, methyl vinyl sulphone, divinyl sulphone, vinyl acetate, vinyl propionate, succinic acid, divinyl ester, N-vinyl pyrrolidone, N-vinyl captrolactam, isobutyl vinyl ether, butane diol- 1,4-divinyl ether, ethyl acrylate, methyl methacrylate, glycol dimethacrylate, ethyl alpha-chloroacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl phosphate, glycol diallyl ether or pentacrythritol tetra allyl ether.  Polymerisatio may be effected by the action of ultra violet light, or in the presence of a catalyst such as methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, tertiary-butyl permaleates, ditertiary butyl peroxide, azo-bisisobutyronitrile, azo-bis-isobutyric acid, dibutyl ester or redox systems containing one of the peroxides and a tertiary amine such as dimethylaniline, diethylaniline or dodecylmercaptan.  Metal driers such as naphthenates, octoates, or, linoleates of iron, cobalt, nickel, manganese, chromium, lead, zinc, cerium, aluminium or calcium may be added and also polymerisation inhibitors such as monohydric or polyhydric phenols such as hydroquinone, resorcinol, pyrocatechol, 2,6-ditertiary-butyl para cresols, or phenylnaphthylamine.  In examples, the tetra-allyl ether of tetramethylol glyoxal diureine is condensed with succinic acid or allyl alcohol and then reacted with the unsaturated polyester resin derived from maleic acid and propylene glycol or from maleic acid, 2,2-dimethyl-1,3 and is then copolymerised with styrene.  The product is a hard tack free polymer and may be moulded to form carriage bodies and boat hulls.